EP0416660A2 - Reinforced film and method of manufacturing same - Google Patents
Reinforced film and method of manufacturing same Download PDFInfo
- Publication number
- EP0416660A2 EP0416660A2 EP90117317A EP90117317A EP0416660A2 EP 0416660 A2 EP0416660 A2 EP 0416660A2 EP 90117317 A EP90117317 A EP 90117317A EP 90117317 A EP90117317 A EP 90117317A EP 0416660 A2 EP0416660 A2 EP 0416660A2
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- Prior art keywords
- fabric
- mat
- film
- plastic
- combination
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/40—Shaping or impregnating by compression not applied
- B29C70/50—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
- B29C70/504—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC] using rollers or pressure bands
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/06—Fibrous reinforcements only
- B29C70/08—Fibrous reinforcements only comprising combinations of different forms of fibrous reinforcements incorporated in matrix material, forming one or more layers, and with or without non-reinforced layers
Definitions
- the present invention relates to reinforced films impervious to rain or other liquids or gases and useful for tarpaulins, boat and truck covers, lawn furniture, awnings, tenting, signs and the like.
- the films of this invention can attain significantly improved properties in terms of resistance to hydrostatic pressure, reduced water absorption and essentially no wicking of moisture.
- the present invention also relates to the manufacture of such films.
- the film includes a polyester open fabric and at least one polyester mat embedded within cured polyvinylchloride (PVC).
- Impervious, reinforced industrial membranes may consist of a reinforcing fabric sandwiched between two films of plastic.
- the fabric principally supplies strength, and the films make the membrane non-porous and impervious.
- Higher tensile strength contributes to higher tear strength and puncture resistance.
- Good tear or breaking strength is necessary to prevent exacerbation of an accidental puncture.
- Other key criteria are resistance to hydrostatic pressure and low wicking by the fabric.
- the open scrim permitted very high adhesion between two films laminated on each side of the fabric because each film readily bonded to the other through the openings of the scrim. Because of this high degree of adhesion between the films, little or no adhesion was required between the film and the yarn of the fabric. The yarns could slide through the membrane very easily to "rope up" and provide a relatively high tear strength. However, because of the few or small number of yarns used to achieve the openness of the weave, the tensile strength was low. Moreover, due to the nature of the open scrim, it was difficult to use liquid coating processes to create two films on either side of these fabrics. Instead, membranes were made by laminating a scrim between two previously prepared films.
- An alternative prior art method for making a non-porous membrane using an open-weave fabric is the rotary screen method.
- a thick paste of very viscous thermoplastic polymer having for example a viscosity on the order of 50,000 centipoise ("cps"), is placed inside a rotating cylinder made of a screen.
- a press or scraper extrudes the paste out of the cylinder where it is transferred to a fabric. If two such rotating cylinders are placed on each side of an open weave fabric, a film can be formed on both sides of it.
- the equipment for this process is expensive and the adhesion of the film to the fabric is not at a maximum because the thick paste does not fully impregnate the yarns of the fabric.
- Tightly woven conventional weaves of fabric were also used in impervious, reinforced industrial membranes in the past for high tensile applications. Because there were essentially no openings in these fabrics, liquid coating processes could be used with them to create films on each side of the fabric. Because of the tight weave, however, it was impossible to create a single unitary film, and there was no adhesion of the film on one side to the film on the other. Strength therefore depended on the adhesion of the film to the yarn. This film-to-yarn adhesion, along with the tight weave, would tend to lock the yarns in place and keep them from sliding, significantly reducing the tear strength of the fabric. That is, the yarns were not able to work together (i.e., "rope-up") to resist the tearing force, but were torn individually.
- U.S. Patent 3,250,662 relates to a modified weave design that was developed in the early 1960s. This fabric utilizes a warp having yarns of two different denier sizes arranged so that two of the smaller denier yarns alternated with the single yarns of the larger denier.
- the fill yarns were laid only on one side of the warp yarn rather than having them interlock between the warp yarn. Because of the nature of the equipment utilized in the late 1960's to provide the new weave design, the fill yarn was inserted in an overlapping crisscross pattern at a five-degree bias angle to the warp yarn.
- a non-porous, reinforced film, impervious to liquids or gases that has the nature of a unitary film and is less susceptible to delamination and otherwise has improved properties.
- the resulting film has a high resistance to hydrostatic pressure and is resistant to water absorption, i.e., is "low-wicking". Preferably, it is essentially non-wicking.
- the present invention is directed to a non-porous, impervious, unitary, reinforced film.
- the film includes an open fabric positioned adjacent at least one light weight porous mat.
- a viscous liquid comprising a thermoformable plastic is coated onto and impregnated into the fabric and mat combination.
- the liquid may for example comprise a carrier liquid in which the plastic is emulsified, dispersed, dissolved or otherwise liquified or suspended.
- the liquid flows through the open fabric and the porous mat; the liquid impregnates yarns of the fabric and surrounds filaments of the mat.
- the plastic is then set in situ on the fabric and mat, for example by a partial curing, by drying, or otherwise greatly reduced its viscosity and any tackiness.
- the impregnated fabric and mat combination is then subjected continuously to heat and pressure by calendering, which forces the plastic (a) to further impregnate and surround fibers of the yarn and filaments of the mat, (b) to close up pores and voids in the combination of fabric and mat impregnated with plastic to create a unitary, continuous, non-porous film, and (c) to embed the fabric/mat combination in the film.
- the plastic thus penetrates through the open fabric and porous mat and adheres to the yarns of the fabric and the filaments of the mat.
- the resultant product of this invention is an homogeneous, unitary film of plastic, the reinforcement is fully embedded therein, and the surface of the film is not pierced by the fabric or the mat and has no other discontinuities.
- the present invention is also directed to the method of manufacture of the impervious film.
- the film is manufactured in a continuous process in which a viscous liquid (for example, an emulsion, dispersion, solution or other suspension), comprising a thermoformable plastic is coated onto and impregnated into an open fabric and at least one light weight, porous mat.
- a viscous liquid for example, an emulsion, dispersion, solution or other suspension
- a thermoformable plastic comprising a thermoformable plastic is coated onto and impregnated into an open fabric and at least one light weight, porous mat.
- a wet lamination process may also be used.
- the impregnated fabric and impregnated mat or mats are in side-by-side relation and form a combination that carries the viscous liquid.
- the viscous liquid is set in situ to from an intermediate combination of impregnated fabric and mat that still may contain pores.
- This intermediate impregnated combination is then subjected continuously to sufficient heat and pressure in a calendering operation to deform the plastic, force it further into the yarn and mat or mats, close pores and voids, and bring plastic on each side of the combination into adhesive contact with plastic on the other through openings in the fabric and pores in the mat.
- Such plastics, mats, and steps are selected and performed so as to create an impervious, low-wicking, reinforced, continuous, unitary film.
- the continuous nature of the calendering results in the plastic impregnating and embedding the fabric and mats in a continuous, unitary film, and the resultant film is essentially non-porous and free from internal voids.
- the film 5 includes an open fabric 10 and a porous mat 20.
- the open fabric 10 is preferably a weft inserted warp knit (WIWK) polyethylene terephthalate (PET) scrim.
- WIWK weft inserted warp knit
- PET polyethylene terephthalate
- Other materials may be used such as polyester, polyamide, aromatic amide, polyethylene, glass, fiberglass, and nylon.
- Other fabrics, such as those made by a woven or non-woven process, may be used.
- the open fabric 10 may have four to twenty yarns per inch in either the machine direction or the cross machine direction. However, it is preferred to have six to nine yarns per inch in the machine direction and six to eighteen yarns per inch in the cross machine direction. It may have a weight of one to eight ounces per square yard, but preferably is three to 4.2 ounces per square yard.
- the mat 20 is generally a single layer of randomly oriented continuous or staple filaments, preferably, of polyester.
- the polyester mat 20 may be a spunwoven polyester sheet weighing on the order of 0.2 to 1.5 ounces per square yard, with 0.4 to 0.7 ounces per square yard preferred.
- a typical material to be used is the polyester mat known under the trademark Reemay.
- Other materials that may be used for the mat 20 are polyamide, polyethylene, glass, fiberglass, nylon and other fabrics suitable for use in the instant invention.
- the polyester mat 20 bridges the gap between the yarns of the polyester fabric 10 and holds enough applied thermoformable plastic 30 such that after calendering, the coating is forced through the mat and the yarns of the fabric with no pinholes remaining in the final product.
- the polyester fabric 10 and the polyester mat 20 are coated with a suitable thermoformable plastic coating 30.
- Preferred materials for coating 30 are polyvinylchlorides such as PVC plastisol and PVC latex, having melting temperatures ranging from 275°F to 425°F.
- Other polymeric materials that may be used include but are not limited to polychloroprene, polyurethane, polyethylene, and acrylics, acetate-latex, and chlorosulfonated polyethylene.
- the resulting film 5 is one having all interstices filled, the surfaces of which are smooth and in which no voids or air bubbles exist.
- the resulting film 5 is water impervious, strong, non-porous and has the features of having a high resistance to hydrostatic pressure and being resistant to water absorption, i.e. it is "low-wicking". Hydrostatic resistance above 200 psi is preferred as measured by ASTM test no. D-3393.
- a material of this type lends itself particularly well to use as a waterproofing membrane for tarpaulins, boat and truck covers, lawn furniture, awnings, and the like.
- Wicking may be tested by cutting an edge of a reinforced film or membrane, holding the cut edge in contact with the surface of a testing liquid, such as water containing a dye, for a short period of time, withdrawing the fabric edge from the liquid, and observing how far the liquid has been drawn by capillary action along the yarn up into the film or membrane. While industrial membranes of the prior art will draw the testing liquid up into the membrane as much as an inch, films of this invention are essentially non-wicking; that is, they draw essentially no liquid into the film when tested as described.
- a testing liquid such as water containing a dye
- a liquid absorption test may also be performed in which a sample sheet of fabric of specified size is soaked in a test liquid for a set period. The sheet is then removed and the amount of liquid adsorbed, if any, is measured accordingly.
- the films of this invention give improved performance relative to the prior art in this test as well.
- additional fabrics or mats may be included in or adjacent to the film.
- Fig. 2 illustrates an embodiment of an apparatus for performing a method of manufacture according to the present invention which includes a feed roller for feeding the WIWK polyester fabric 10 through a liquid viscous bath 42.
- the kind of roller used will depend on the type of material used. For instance, steel or rubber or other suitable materials may be used.
- the liquid bath 42, held in container 40, is generally a low viscosity mix. Although viscosities on the order of 50 to 10,000 centipoise (cps) may be used, it is preferred to use coatings having on the order to 1000 to 4000 cps, with 2000 to 3000 cps being the most preferred.
- the plastic in the liquid should be thermoformable so that it may be calendered at a later stage.
- Container 40 is larger than roller 60 so that any excess liquid will drain back to the liquid bath 42.
- a preferred liquid level of the bath is such that a depth on the order of two to three inches may be maintained.
- the liquid bath preferably contains approximately 85% solids to liquids (e.g. organosol to plastisol). Additives may be introduced as necessary to obtain desired properties in the resulting film such as translucency, opacity, flame retardancy, and flexibility. Also, surfactants or wetting agents, such as Union Carbide silicone surfactant Sag 47, may be added as required, depending for example on the fabric and mat being used and on the viscosity of the liquid.
- additives e.g. organosol to plastisol.
- surfactants or wetting agents such as Union Carbide silicone surfactant Sag 47, may be added as required, depending for example on the fabric and mat being used and on the viscosity of the liquid.
- polyester mat 20 is added onto the resulting coated WIWK polyester fabric 50.
- Polyester mat 20 and the coated fabric 50 are fed into the padder roller 70 adjacent the feed roller 60.
- the padder roller 70 provides a sufficiently narrow nip with roller 60 to distribute the liquid uniformly over and into the fabric and mat combination.
- the viscosity of the liquid and the size of the gap between rolls 60 and 70 are adjusted such that a large amount of thermoformable plastic is picked up.
- the dry weight percent of plastic picked up that is, weight of plastic less solvents or other liquids in the coating liquid 42, or "DPU" be 100 to 800% relative to the weight of the fabric/mat combination. It is preferred that the DPU weight of the thermoformable plastic carried on the combination be 200 to 500%, with 170 to 280% being the most preferred.
- polyester mat 20 is fed onto coated fabric 50 after the liquid bath 42
- equivalent methods such as having the polyester mat 20 fed along with the polyester fabric 10 into the liquid coating bath 42 at the initial stages of the process, or having the mat 20 led into the bath 42 to later combined with the fabric 10, may be used.
- the open fabric and mat combination 52, now impregnated, is fed to a setting stage 80.
- setting may refer to drying, partially curing the plastic as by the application of heat, or otherwise greatly reducing the viscosity and any tackiness of the liquid comprising plastic.
- the fabric at the setting stage may be heated to a temperature on the order of about 290°F.
- the setting stage 80 may include ovens or heated rollers or cans. After this stage, little or nothing remains in the impregnated combination of fabric and mat of any carrier liquid used in liquid 42, and the intermediate combination is still somewhat porous.
- Prior art polyester open fabrics without a mat at this stage would have air permeability indices of over 1000 (cubic feet)(seconds) per square foot.
- the inventive fabric using a mat may have an air permeability index of 0 to 5000 at this stage, it is preferred that the fabric 54 have an air permeability index of 0 to 300 with approximately 150 being the most preferred.
- the intermediate combination 54 is then fed to a calendering stage 95.
- the calendering stage 95 includes nip rollers 90 and 100. Calendering is typically done at an elevated temperature.
- roller 100 is a hot roller with the mat 20 contacting the roller 100, as explained below. Roller 100 may be heated on the order of 250 to 450°F, but the exact temperature depends on the plastic used and the speed of the process. It is preferred to apply a temperature of about 380 to 410°F.
- the roller 90 may be rubber coated.
- the plastic tends to flow toward heat.
- the plastic closes up any pores and encloses the filaments of the mat, reducing or eliminating discontinuities at the exterior surface and creating a continuous surface for the film. Any tendency of the mat to break through the surface of the film is thus reduced by the tendency of the plastic to move toward the heat, and the mat therefore tends to be embedded within the film.
- the calendering stage 95 has significant effects. It flattens out the yarns. It has a tendency to drive the plastic between the filaments of the yarn and the mat. It causes the coating to spread out uniformly to create a unitary film that is impervious and free of voids. It also forces the plastic on either side of the fabric and mat combination through openings in the fabric and pores in the mat into adhesive contact with plastic on the other side.
- the calendering state 95 also causes the thermoplastic coating to flow and close all "windows" that may have existed in the combination at 54 and promotes adhesion of the polyester fabric 10 to the polyester mat 20.
- the applied pressure using rollers about 30 inches in diameter may be about 50 to 300 pounds per linear inch. It is preferred to apply a pressure of about 150 to 200 pounds per linear inch.
- the polyester mat 20 serves the further function of cushioning the polyester fabric 10.
- This cushioning allows a higher pressure to be maintained at the calendering stage 95 and promotes and enables the calendering to have the desired effects. Moreover, any voids or openings are also closed. The higher pressure results in a non-porous, unitary reinforced film 5 having all "windows" and all pores within those windows filled in.
- the polyester fabric or scrim and the polyester mat receive a viscous polyvinylchloride in liquid form.
- the mat holds the polyvinylchloride in the spaces between the yarns of the scrim.
- the impregnated combination is first set or dried and then led to a nip (calendered) to create a cured, reinforced polyvinylchloride film from the impregnated and coated polyester scrim and polyester mat combination.
- the resulting film is the water impervious, reinforced, unitary film of the instant invention.
- the open fabric and the mat may be laminated together before they are impregnated (for example, with heat and pressure), preferably they are not so laminated, but rather led separately into contact with the thermoformable plastic comprising viscous liquid. Preferably, only thereafter is the liquid set to laminate the fabric and the mat together. This wet impregnation process before lamination of the mat and fabric as by heat is believed to result in better impregnation of the mat and the yarns of the fabric and in better resultant properties.
- Such a uniform film 5 provides the features of very little or no wicking and very high resistance to hydrostatic pressure.
- a reinforced film impervious to water and being essentially void free with little or no wicking is prepared as follows:
- a warp inserted weft knit polyester scrim weighing three to three and one half ounces per square yard, made from 1000 denier continuous filament polyester and having 9 x 12 yarns per inch, is fed through a PVC plastisol bath of viscosity 2500 cps at a depth of two to three inches.
- the plastisol bath contains 85% solids (organosol to plastisol).
- the coated scrim is fed separately or jointly with a polyester met that weighs one half ounce per square yard through nip rollers approximately twelve inches in diameter. The nip rollers squeeze the fabric such that the remaining liquid from the coating bath fills the majority of windows in the fabric.
- the DPU is 170-220%.
- the fabric is then fed across can dryers or rollers at a temperature of about 290°F to dry and set the impregnated combination.
- the air permeability at this point is 400 to 700 (cubic feet)(seconds) per square foot. Little or no carrier liquid remains after this stage.
- the combination is then fed to two 30 inch diameter nip rollers (one rubber, one steel).
- the steel roller is heated to approximately 400°F.
- the nip rollers apply pressure at approximately 150 to 200 pounds per linear inch such that the plastic flows to further impregnate the yarns, to penetrate the mat and to fill all voids, interstices and pores.
- the rubber roller is crowned at the center to provide uniform pressure across the width of the roll even at the pressure use.
- the plastic is cured by the heat.
- the resulting reinforced, unitary film is non-porous, water impermeable, and low-wicking.
- Fig. 3 is a partial view of another embodiment of the apparatus for use in applying the manufacturing method for this invention. Like reference numerals have been used for like elements as in the Fig. 2 embodiment and further discussion will be made only as necessary to explain the features of the embodiment of Fig. 3.
- a WIWK polyester fabric 10 is fed along with a polyester mat 21 on feed roller 60 into liquid coating bath 42 held in container 40.
- the polyester mat 21 has substantially the same properties as polyester mat 20 discussed with reference to the Fig. 2 embodiment.
- the mat 20 is then introduced to the fabric 10 and mat 21 combination leaving the liquid coating bath 42.
- the mat 20 is fed to the side opposite mat 21, with fabric 10 in between.
- These three layers are then fed between feed roller 60 and nip roller 70.
- the resulting combination 56 from this stage is then fed to the setting stage and calendering stage as in the embodiment of Fig. 2.
- mat 21 and mat 20 are both introduced along with fabric 10 at the liquid application stage 42
- the present invention is not intended to be limited to this preferred embodiment.
- either one of the mats 20 and 21 may individually be fed adjacent to the fabric 10 at this stage.
- more than two mats could be introduced at this stage, as well.
- many mats as are desired in the resulting fabric may be introduced at this stage by applying the novel concepts of the instant invention.
- Fig. 4 shows a resulting impervious film 15 according to the embodiment shown in Fig. 3. As will be discussed later, Fig. 4 also shows a resulting impervious film 15 according to the embodiment shown in Fig. 5, as well.
- the resulting fabric 15 includes an open fabric 10, mat 20 and mat 21.
- This fabric and these mats may have similar properties as those discussed with respect to the embodiment of Fig. 1. Accordingly, further comment with respect to the properties thereof will not be made and reference may be had to the earlier discussion.
- the mats 20 and 21 bridge the gap between the yarns of the fabric 10 and hold enough applied thermoformable plastic 30 such that after calendering, the coating is forced throughout the mat and the yarns of the fabric and no pinholes remain in the final product.
- the resulting reinforced film 15 is one having all interstices filled, the surfaces of which are smooth, with no voids or air bubbles existing.
- the resulting film 15 is water impervious, strong, non-porous and has the feature of having a high resistance to hydrostatic pressure.
- FIG. 5 shows yet another embodiment of apparatus for use in applying the manufacturing method of the instant invention.
- Like reference numerals have been used for like elements as used in previous embodiments and further discussion will be made only as necessary for explanation of the instant embodiment.
- Fabric 10 is fed to the liquid bath 42 held in container 40. From the bath, the fabric is fed towards nip stage 140 that includes nip rollers 120 and 130. At this stage mats 20 and 21 are fed from suitable feed rollers 110 along guide rollers 105 towards nip rollers 120 130. The combination 53 is then led to later stages where is it set and calendered, typically at elevated temperatures, as discussed earlier.
- the resulting film 15 as shown in Fig. 4 may be attained.
- Film 15 includes mats 20 and 21 on either side of fabric 10, with suitable plastic coating 30 permeating the layers.
- the resulting reinforced film 15 is one having all interstices filled and smooth surfaces, with essentially no voids or air bubbles.
- the resulting film 15 is also water impervious, strong, non-porous and has the feature of having a high hydrostatic pressure resistance and being resistant to water absorption, i.e., it is "low-wicking".
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Abstract
Description
- The present invention relates to reinforced films impervious to rain or other liquids or gases and useful for tarpaulins, boat and truck covers, lawn furniture, awnings, tenting, signs and the like. The films of this invention can attain significantly improved properties in terms of resistance to hydrostatic pressure, reduced water absorption and essentially no wicking of moisture. The present invention also relates to the manufacture of such films. In a preferred embodiment, the film includes a polyester open fabric and at least one polyester mat embedded within cured polyvinylchloride (PVC).
- Impervious, reinforced industrial membranes may consist of a reinforcing fabric sandwiched between two films of plastic. The fabric principally supplies strength, and the films make the membrane non-porous and impervious. Higher tensile strength contributes to higher tear strength and puncture resistance. Good tear or breaking strength is necessary to prevent exacerbation of an accidental puncture. Other key criteria are resistance to hydrostatic pressure and low wicking by the fabric.
- In the past, primarily two kinds of fabric were available for the impervious, reinforced industrial membrane industry. They were open, loose scrim (woven and non-woven) and very tightly woven, conventional, plain weave fabric.
- The open scrim permitted very high adhesion between two films laminated on each side of the fabric because each film readily bonded to the other through the openings of the scrim. Because of this high degree of adhesion between the films, little or no adhesion was required between the film and the yarn of the fabric. The yarns could slide through the membrane very easily to "rope up" and provide a relatively high tear strength. However, because of the few or small number of yarns used to achieve the openness of the weave, the tensile strength was low. Moreover, due to the nature of the open scrim, it was difficult to use liquid coating processes to create two films on either side of these fabrics. Instead, membranes were made by laminating a scrim between two previously prepared films. For example, in making prior art membranes using open weave scrim fabrics, two PVC films were first created by extrusion, cured and then laminated to each side of a polyester scrim, perhaps with an adhesive between them. Such a lamination technique did not create a single, unitary film, and if not completely successful, resulted in a membrane that delaminated easily when stressed. Further, if any bit of delamination occurred, the yarns of the fabric tended to wick moisture into the membrane. Wicking (allowing moisture to seep into and along the yarns at the edges, cracks or openings) exacerbates the problem of delamination.
- An alternative prior art method for making a non-porous membrane using an open-weave fabric is the rotary screen method. In this method, a thick paste of very viscous thermoplastic polymer, having for example a viscosity on the order of 50,000 centipoise ("cps"), is placed inside a rotating cylinder made of a screen. A press or scraper extrudes the paste out of the cylinder where it is transferred to a fabric. If two such rotating cylinders are placed on each side of an open weave fabric, a film can be formed on both sides of it. However, the equipment for this process is expensive and the adhesion of the film to the fabric is not at a maximum because the thick paste does not fully impregnate the yarns of the fabric.
- Tightly woven conventional weaves of fabric were also used in impervious, reinforced industrial membranes in the past for high tensile applications. Because there were essentially no openings in these fabrics, liquid coating processes could be used with them to create films on each side of the fabric. Because of the tight weave, however, it was impossible to create a single unitary film, and there was no adhesion of the film on one side to the film on the other. Strength therefore depended on the adhesion of the film to the yarn. This film-to-yarn adhesion, along with the tight weave, would tend to lock the yarns in place and keep them from sliding, significantly reducing the tear strength of the fabric. That is, the yarns were not able to work together (i.e., "rope-up") to resist the tearing force, but were torn individually.
- Some attempts to manufacture an improved fabric have addressed the fabric weave. For instance, U.S. Patent 3,250,662 relates to a modified weave design that was developed in the early 1960s. This fabric utilizes a warp having yarns of two different denier sizes arranged so that two of the smaller denier yarns alternated with the single yarns of the larger denier.
- In a further weave design, the fill yarns were laid only on one side of the warp yarn rather than having them interlock between the warp yarn. Because of the nature of the equipment utilized in the late 1960's to provide the new weave design, the fill yarn was inserted in an overlapping crisscross pattern at a five-degree bias angle to the warp yarn.
- In another prior art weave design, the fill yarns were inserted parallel to each other and perpendicular to the warp. This weave came to be known in the industry as weft inserted warp knit (WIWK) fabric. This weave gave better tear and tensile strength, but can be further improved by use of the present invention.
- Accordingly, it is one object of the present invention to manufacture a non-porous, reinforced film, impervious to liquids or gases, that has the nature of a unitary film and is less susceptible to delamination and otherwise has improved properties.
- It is another objection of the present invention to provide an impervious, reinforced, unitary film including an open fabric, sometimes referred to as a grid, web or scrim, provided with at least one light weight, porous mat and impregnated with plastic. The resulting film has a high resistance to hydrostatic pressure and is resistant to water absorption, i.e., is "low-wicking". Preferably, it is essentially non-wicking.
- It is still another object of the instant invention to provide a process and apparatus whereby the above-described film may be made using an uncomplicated arrangement of machinery.
- These and other objects that will become apparent and may be better understood by the detailed description provided below.
- The present invention is directed to a non-porous, impervious, unitary, reinforced film. The film includes an open fabric positioned adjacent at least one light weight porous mat. A viscous liquid comprising a thermoformable plastic is coated onto and impregnated into the fabric and mat combination. The liquid may for example comprise a carrier liquid in which the plastic is emulsified, dispersed, dissolved or otherwise liquified or suspended. The liquid flows through the open fabric and the porous mat; the liquid impregnates yarns of the fabric and surrounds filaments of the mat. The plastic is then set in situ on the fabric and mat, for example by a partial curing, by drying, or otherwise greatly reduced its viscosity and any tackiness. The impregnated fabric and mat combination is then subjected continuously to heat and pressure by calendering, which forces the plastic (a) to further impregnate and surround fibers of the yarn and filaments of the mat, (b) to close up pores and voids in the combination of fabric and mat impregnated with plastic to create a unitary, continuous, non-porous film, and (c) to embed the fabric/mat combination in the film. The plastic thus penetrates through the open fabric and porous mat and adheres to the yarns of the fabric and the filaments of the mat. Preferably the resultant product of this invention is an homogeneous, unitary film of plastic, the reinforcement is fully embedded therein, and the surface of the film is not pierced by the fabric or the mat and has no other discontinuities.
- The present invention is also directed to the method of manufacture of the impervious film. The film is manufactured in a continuous process in which a viscous liquid (for example, an emulsion, dispersion, solution or other suspension), comprising a thermoformable plastic is coated onto and impregnated into an open fabric and at least one light weight, porous mat. A wet lamination process may also be used. The impregnated fabric and impregnated mat or mats are in side-by-side relation and form a combination that carries the viscous liquid. The viscous liquid is set in situ to from an intermediate combination of impregnated fabric and mat that still may contain pores. This intermediate impregnated combination is then subjected continuously to sufficient heat and pressure in a calendering operation to deform the plastic, force it further into the yarn and mat or mats, close pores and voids, and bring plastic on each side of the combination into adhesive contact with plastic on the other through openings in the fabric and pores in the mat. Such plastics, mats, and steps are selected and performed so as to create an impervious, low-wicking, reinforced, continuous, unitary film.
- In the process of the present invention, the continuous nature of the calendering results in the plastic impregnating and embedding the fabric and mats in a continuous, unitary film, and the resultant film is essentially non-porous and free from internal voids.
- A better understanding of these and other advantages of the present invention, as well as objects attained for its use, may be had by reference to the drawings which form a further part hereto and to the accompanying descriptive matter in which there are illustrated and described preferred embodiments of the invention.
-
- Fig. 1 is a cross-sectional view of an impervious, unitary film according to one embodiment of the present invention.
- Fig. 2 is an embodiment of apparatus for use in applying the manufacturing method of this invention.
- Fig. 3 is a partial view of another embodiment of apparatus for use in applying the manufacturing method of this invention.
- Fig. 4 is a cross-sectional view of an impervious, unitary film according to another embodiment of the present invention.
- Fig. 5 is yet another embodiment of apparatus for use in applying the manufacturing method of this invention.
- Referring now to Fig. 1, the impervious, reinforced,
unitary film 5 according to one embodiment of the invention is illustrated. Thefilm 5 includes anopen fabric 10 and aporous mat 20. Theopen fabric 10 is preferably a weft inserted warp knit (WIWK) polyethylene terephthalate (PET) scrim. Other materials may be used such as polyester, polyamide, aromatic amide, polyethylene, glass, fiberglass, and nylon. Other fabrics, such as those made by a woven or non-woven process, may be used. Theopen fabric 10 may have four to twenty yarns per inch in either the machine direction or the cross machine direction. However, it is preferred to have six to nine yarns per inch in the machine direction and six to eighteen yarns per inch in the cross machine direction. It may have a weight of one to eight ounces per square yard, but preferably is three to 4.2 ounces per square yard. - The
mat 20 is generally a single layer of randomly oriented continuous or staple filaments, preferably, of polyester. Thepolyester mat 20 may be a spunwoven polyester sheet weighing on the order of 0.2 to 1.5 ounces per square yard, with 0.4 to 0.7 ounces per square yard preferred. A typical material to be used is the polyester mat known under the trademark Reemay. Other materials that may be used for themat 20 are polyamide, polyethylene, glass, fiberglass, nylon and other fabrics suitable for use in the instant invention. Thepolyester mat 20 bridges the gap between the yarns of thepolyester fabric 10 and holds enough applied thermoformable plastic 30 such that after calendering, the coating is forced through the mat and the yarns of the fabric with no pinholes remaining in the final product. - The
polyester fabric 10 and thepolyester mat 20 are coated with a suitable thermoformableplastic coating 30. Preferred materials for coating 30 are polyvinylchlorides such as PVC plastisol and PVC latex, having melting temperatures ranging from 275°F to 425°F. Other polymeric materials that may be used include but are not limited to polychloroprene, polyurethane, polyethylene, and acrylics, acetate-latex, and chlorosulfonated polyethylene. - The resulting
film 5 is one having all interstices filled, the surfaces of which are smooth and in which no voids or air bubbles exist. The resultingfilm 5 is water impervious, strong, non-porous and has the features of having a high resistance to hydrostatic pressure and being resistant to water absorption, i.e. it is "low-wicking". Hydrostatic resistance above 200 psi is preferred as measured by ASTM test no. D-3393. A material of this type lends itself particularly well to use as a waterproofing membrane for tarpaulins, boat and truck covers, lawn furniture, awnings, and the like. - Wicking may be tested by cutting an edge of a reinforced film or membrane, holding the cut edge in contact with the surface of a testing liquid, such as water containing a dye, for a short period of time, withdrawing the fabric edge from the liquid, and observing how far the liquid has been drawn by capillary action along the yarn up into the film or membrane. While industrial membranes of the prior art will draw the testing liquid up into the membrane as much as an inch, films of this invention are essentially non-wicking; that is, they draw essentially no liquid into the film when tested as described.
- A liquid absorption test may also be performed in which a sample sheet of fabric of specified size is soaked in a test liquid for a set period. The sheet is then removed and the amount of liquid adsorbed, if any, is measured accordingly. The films of this invention give improved performance relative to the prior art in this test as well.
- In addition to the creation of a film comprising an open fabric and at least one mat, additional fabrics or mats may be included in or adjacent to the film.
- Fig. 2 illustrates an embodiment of an apparatus for performing a method of manufacture according to the present invention which includes a feed roller for feeding the
WIWK polyester fabric 10 through a liquidviscous bath 42. The kind of roller used will depend on the type of material used. For instance, steel or rubber or other suitable materials may be used. - The
liquid bath 42, held incontainer 40, is generally a low viscosity mix. Although viscosities on the order of 50 to 10,000 centipoise (cps) may be used, it is preferred to use coatings having on the order to 1000 to 4000 cps, with 2000 to 3000 cps being the most preferred. The plastic in the liquid should be thermoformable so that it may be calendered at a later stage. -
Container 40 is larger thanroller 60 so that any excess liquid will drain back to theliquid bath 42. A preferred liquid level of the bath is such that a depth on the order of two to three inches may be maintained. Although the coating step has been depicted as a dipping stage, other conventional coating techniques may be applied including, but not limited to, brushing or spraying so that an adequate coat is applied. - The liquid bath preferably contains approximately 85% solids to liquids (e.g. organosol to plastisol). Additives may be introduced as necessary to obtain desired properties in the resulting film such as translucency, opacity, flame retardancy, and flexibility. Also, surfactants or wetting agents, such as Union Carbide silicone surfactant Sag 47, may be added as required, depending for example on the fabric and mat being used and on the viscosity of the liquid.
- The
polyester mat 20 is added onto the resulting coatedWIWK polyester fabric 50.Polyester mat 20 and thecoated fabric 50 are fed into thepadder roller 70 adjacent thefeed roller 60. - The
padder roller 70 provides a sufficiently narrow nip withroller 60 to distribute the liquid uniformly over and into the fabric and mat combination. The viscosity of the liquid and the size of the gap betweenrolls coating liquid 42, or "DPU") be 100 to 800% relative to the weight of the fabric/mat combination. It is preferred that the DPU weight of the thermoformable plastic carried on the combination be 200 to 500%, with 170 to 280% being the most preferred. - Although it is shown that the
polyester mat 20 is fed onto coatedfabric 50 after theliquid bath 42, it is within the concept of the instant invention that equivalent methods, such as having thepolyester mat 20 fed along with thepolyester fabric 10 into theliquid coating bath 42 at the initial stages of the process, or having themat 20 led into thebath 42 to later combined with thefabric 10, may be used. - The open fabric and
mat combination 52, now impregnated, is fed to asetting stage 80. As used herein, setting may refer to drying, partially curing the plastic as by the application of heat, or otherwise greatly reducing the viscosity and any tackiness of the liquid comprising plastic. The fabric at the setting stage may be heated to a temperature on the order of about 290°F. The settingstage 80 may include ovens or heated rollers or cans. After this stage, little or nothing remains in the impregnated combination of fabric and mat of any carrier liquid used inliquid 42, and the intermediate combination is still somewhat porous. Prior art polyester open fabrics without a mat at this stage would have air permeability indices of over 1000 (cubic feet)(seconds) per square foot. Although the inventive fabric using a mat may have an air permeability index of 0 to 5000 at this stage, it is preferred that thefabric 54 have an air permeability index of 0 to 300 with approximately 150 being the most preferred. - The
intermediate combination 54 is then fed to acalendering stage 95. Thecalendering stage 95 includes niprollers roller 100 is a hot roller with themat 20 contacting theroller 100, as explained below.Roller 100 may be heated on the order of 250 to 450°F, but the exact temperature depends on the plastic used and the speed of the process. It is preferred to apply a temperature of about 380 to 410°F. Theroller 90 may be rubber coated. - It is preferred to place the mat against the
hot roller 100 at the nip because it is believed the plastic tends to flow toward heat. By so arranging the mat and the hot roller, the plastic closes up any pores and encloses the filaments of the mat, reducing or eliminating discontinuities at the exterior surface and creating a continuous surface for the film. Any tendency of the mat to break through the surface of the film is thus reduced by the tendency of the plastic to move toward the heat, and the mat therefore tends to be embedded within the film. - Because of the pressure gradient at the nip, the
calendering stage 95 has significant effects. It flattens out the yarns. It has a tendency to drive the plastic between the filaments of the yarn and the mat. It causes the coating to spread out uniformly to create a unitary film that is impervious and free of voids. It also forces the plastic on either side of the fabric and mat combination through openings in the fabric and pores in the mat into adhesive contact with plastic on the other side. - The
calendering state 95 also causes the thermoplastic coating to flow and close all "windows" that may have existed in the combination at 54 and promotes adhesion of thepolyester fabric 10 to thepolyester mat 20. The applied pressure using rollers about 30 inches in diameter may be about 50 to 300 pounds per linear inch. It is preferred to apply a pressure of about 150 to 200 pounds per linear inch. - At this stage, the
polyester mat 20 serves the further function of cushioning thepolyester fabric 10. This cushioning allows a higher pressure to be maintained at thecalendering stage 95 and promotes and enables the calendering to have the desired effects. Moreover, any voids or openings are also closed. The higher pressure results in a non-porous, unitary reinforcedfilm 5 having all "windows" and all pores within those windows filled in. - In a preferred embodiment of the present invention, the polyester fabric or scrim and the polyester mat receive a viscous polyvinylchloride in liquid form. The mat holds the polyvinylchloride in the spaces between the yarns of the scrim. The impregnated combination is first set or dried and then led to a nip (calendered) to create a cured, reinforced polyvinylchloride film from the impregnated and coated polyester scrim and polyester mat combination. The resulting film is the water impervious, reinforced, unitary film of the instant invention.
- While the open fabric and the mat may be laminated together before they are impregnated (for example, with heat and pressure), preferably they are not so laminated, but rather led separately into contact with the thermoformable plastic comprising viscous liquid. Preferably, only thereafter is the liquid set to laminate the fabric and the mat together. This wet impregnation process before lamination of the mat and fabric as by heat is believed to result in better impregnation of the mat and the yarns of the fabric and in better resultant properties.
- Such a
uniform film 5 provides the features of very little or no wicking and very high resistance to hydrostatic pressure. - The following Example is illustrative of the invention.
- A reinforced film impervious to water and being essentially void free with little or no wicking is prepared as follows:
- A warp inserted weft knit polyester scrim, weighing three to three and one half ounces per square yard, made from 1000 denier continuous filament polyester and having 9 x 12 yarns per inch, is fed through a PVC plastisol bath of viscosity 2500 cps at a depth of two to three inches. The plastisol bath contains 85% solids (organosol to plastisol). The coated scrim is fed separately or jointly with a polyester met that weighs one half ounce per square yard through nip rollers approximately twelve inches in diameter. The nip rollers squeeze the fabric such that the remaining liquid from the coating bath fills the majority of windows in the fabric. The DPU is 170-220%.
- The fabric is then fed across can dryers or rollers at a temperature of about 290°F to dry and set the impregnated combination. The air permeability at this point is 400 to 700 (cubic feet)(seconds) per square foot. Little or no carrier liquid remains after this stage.
- The combination is then fed to two 30 inch diameter nip rollers (one rubber, one steel). The steel roller is heated to approximately 400°F. The nip rollers apply pressure at approximately 150 to 200 pounds per linear inch such that the plastic flows to further impregnate the yarns, to penetrate the mat and to fill all voids, interstices and pores. The rubber roller is crowned at the center to provide uniform pressure across the width of the roll even at the pressure use. The plastic is cured by the heat. The resulting reinforced, unitary film is non-porous, water impermeable, and low-wicking.
- Fig. 3 is a partial view of another embodiment of the apparatus for use in applying the manufacturing method for this invention. Like reference numerals have been used for like elements as in the Fig. 2 embodiment and further discussion will be made only as necessary to explain the features of the embodiment of Fig. 3.
- In this embodiment, a
WIWK polyester fabric 10 is fed along with apolyester mat 21 onfeed roller 60 intoliquid coating bath 42 held incontainer 40. Thepolyester mat 21 has substantially the same properties aspolyester mat 20 discussed with reference to the Fig. 2 embodiment. Optionally, themat 20 is then introduced to thefabric 10 andmat 21 combination leaving theliquid coating bath 42. Thus, themat 20, is fed to the side oppositemat 21, withfabric 10 in between. These three layers are then fed betweenfeed roller 60 and niproller 70. The resultingcombination 56 from this stage is then fed to the setting stage and calendering stage as in the embodiment of Fig. 2. - Although it has been shown that
mat 21 andmat 20 are both introduced along withfabric 10 at theliquid application stage 42, the present invention is not intended to be limited to this preferred embodiment. In fact, either one of themats fabric 10 at this stage. In addition, more than two mats could be introduced at this stage, as well. As many mats as are desired in the resulting fabric may be introduced at this stage by applying the novel concepts of the instant invention. - Fig. 4 shows a resulting
impervious film 15 according to the embodiment shown in Fig. 3. As will be discussed later, Fig. 4 also shows a resultingimpervious film 15 according to the embodiment shown in Fig. 5, as well. - The resulting
fabric 15 includes anopen fabric 10,mat 20 andmat 21. This fabric and these mats may have similar properties as those discussed with respect to the embodiment of Fig. 1. Accordingly, further comment with respect to the properties thereof will not be made and reference may be had to the earlier discussion. Themats fabric 10 and hold enough applied thermoformable plastic 30 such that after calendering, the coating is forced throughout the mat and the yarns of the fabric and no pinholes remain in the final product. - The resulting reinforced
film 15 is one having all interstices filled, the surfaces of which are smooth, with no voids or air bubbles existing. The resultingfilm 15 is water impervious, strong, non-porous and has the feature of having a high resistance to hydrostatic pressure. - Fig. 5 shows yet another embodiment of apparatus for use in applying the manufacturing method of the instant invention. Like reference numerals have been used for like elements as used in previous embodiments and further discussion will be made only as necessary for explanation of the instant embodiment.
-
Fabric 10 is fed to theliquid bath 42 held incontainer 40. From the bath, the fabric is fed towards nipstage 140 that includes niprollers stage mats suitable feed rollers 110 alongguide rollers 105 towards niprollers 120 130. Thecombination 53 is then led to later stages where is it set and calendered, typically at elevated temperatures, as discussed earlier. - As discussed with respect to the previous embodiment of Fig. 3, it is within the concepts of the instant invention to feed either of the
mats web 10 at thestage 140. In addition, more than the number of mats shown could be fed, as well. - By utilizing the novel features of the instant invention as shown in Fig. 5, the resulting
film 15 as shown in Fig. 4 may be attained.Film 15 includesmats fabric 10, with suitableplastic coating 30 permeating the layers. The resulting reinforcedfilm 15 is one having all interstices filled and smooth surfaces, with essentially no voids or air bubbles. The resultingfilm 15 is also water impervious, strong, non-porous and has the feature of having a high hydrostatic pressure resistance and being resistant to water absorption, i.e., it is "low-wicking". - As indicated above, the processes discussed are merely representative or processes which could be used to create various fabrics in accordance with the instant invention. It is to be understood that not only the fabrics, but also the processes which have been disclosed, are illustrative only. Therefore, the foregoing detailed description and example are provided for illustrative purposes only and are not intended to be limiting as to the scope of the present invention. Various modifications and variations are contemplated within the scope of the present invention, which is intended to be limited only by the scope of the accompanying claims.
Claims (22)
providing a viscous impregnating liquid comprising a thermoformable plastic;
providing an open fabric;
providing at least one light weight, porous mat;
impregnating the fabric and the mat with the liquid and forming a side by side combination of impregnated fabric and mat;
setting the plastic in situ on the impregnated combination of fabric and mat;
calendering the set combination of plastic, fabric and mat continuously with sufficient heat and pressure to deform the plastic;
deforming the set plastic to create a non-porous, impervious, continuous, low-wicking, essentially void-free, unitary film having a reinforcement of fabric and mat embedded therein.
an open fabric comprising yarns;
at least one light weight porous mat comprising filaments; and
a thermoformable plastic impregnating the fabric and the mat;
said plastic, fabric and mat being calendered such that yarns of the fabric and filaments of the mat are impregnated with the plastic and adhere to the plastic and the combination of plastic, fabric and mat forms an impervious, reinforced, unitary film.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US07/403,872 US5057172A (en) | 1989-09-07 | 1989-09-07 | Method of manufacturing a reinforced film |
US403872 | 1989-09-07 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0416660A2 true EP0416660A2 (en) | 1991-03-13 |
EP0416660A3 EP0416660A3 (en) | 1992-07-08 |
EP0416660B1 EP0416660B1 (en) | 1997-05-02 |
Family
ID=23597274
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP90117317A Expired - Lifetime EP0416660B1 (en) | 1989-09-07 | 1990-09-07 | Reinforced film and method of manufacturing same |
Country Status (5)
Country | Link |
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US (1) | US5057172A (en) |
EP (1) | EP0416660B1 (en) |
AT (1) | ATE152395T1 (en) |
CA (1) | CA2024860A1 (en) |
DE (1) | DE69030609T2 (en) |
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EP0922560A1 (en) * | 1997-12-10 | 1999-06-16 | Société de Production de Valenciennes, SARL | Process for making a surface covering, processing means therefor and surface coverings produced therewith |
WO2002022346A2 (en) * | 2000-09-12 | 2002-03-21 | Kemlite Company, Inc. | Tear-resistant fiberglass reinforced plastic panel and method of manufacturing such panels |
WO2011098497A1 (en) | 2010-02-09 | 2011-08-18 | Universita' Della Calabria | Zeolite membrane for cellular adhesion, growth and cultures and process for preparation thereof |
US8210953B1 (en) | 2008-11-12 | 2012-07-03 | Whitewater Composites Ltd. | Translucent closed-molded fiber-reinforced plastic and method of making the same |
US20200109570A1 (en) * | 2016-06-21 | 2020-04-09 | MGNT Products Group, LLC | Laminated foam composite backer board for wet space construction |
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US5399419A (en) * | 1989-09-07 | 1995-03-21 | Bay Mills Limited | Reinforced film and method of manufacturing same |
US5314556A (en) * | 1990-05-08 | 1994-05-24 | Bay Mills Limited | Process for manufacturing reinforced roofing membranes |
US5763043A (en) * | 1990-07-05 | 1998-06-09 | Bay Mills Limited | Open grid fabric for reinforcing wall systems, wall segment product and methods of making same |
US5151146A (en) * | 1991-04-02 | 1992-09-29 | Milliken Research Corporation | Method of making a roofing laminate including a triaxial wound nonwoven fiberglass scrim |
US5709766A (en) * | 1995-07-10 | 1998-01-20 | Press; Stuart | Process for preparing a polyurethane coated fabric |
CA2267369C (en) * | 1996-10-23 | 2007-01-23 | Clark A. Higginbotham | Vinylidene difluoride-based coating compositions |
US6315499B1 (en) * | 1999-04-01 | 2001-11-13 | Saint Cobain Technical Fabrics Canada, Ltd. | Geotextile fabric |
CN1416390A (en) | 2000-01-05 | 2003-05-07 | 美国圣戈班技术织物有限公司 | Smooth reinforced cementitious boards and methods of making same |
US6562739B1 (en) | 2000-08-15 | 2003-05-13 | Camo-Tek, Llc | Coated cloth with printed pattern |
US6634850B2 (en) * | 2001-07-31 | 2003-10-21 | Dennis R. Christensen | Tarp application method and apparatus |
US6979479B2 (en) * | 2003-03-14 | 2005-12-27 | Lockheed Martin Corporation | Flexible material for lighter-than-air vehicles |
US20070281570A1 (en) * | 2006-05-30 | 2007-12-06 | Liggett Paul E | Reduced weight flexible laminate material for lighter-than-air vehicles |
US20160221275A1 (en) * | 2015-01-29 | 2016-08-04 | Rohr, Inc. | Method of manufacturing a polyimide film |
US9863071B2 (en) | 2015-01-29 | 2018-01-09 | Milliken & Company | Knit fabric for use in roofing membranes |
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Also Published As
Publication number | Publication date |
---|---|
CA2024860A1 (en) | 1991-03-08 |
EP0416660A3 (en) | 1992-07-08 |
DE69030609D1 (en) | 1997-06-05 |
US5057172A (en) | 1991-10-15 |
DE69030609T2 (en) | 1997-08-14 |
EP0416660B1 (en) | 1997-05-02 |
ATE152395T1 (en) | 1997-05-15 |
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